Selective deposition of aluminum and nitrogen containing material

ABSTRACT

Methods are provided for selectively depositing Al and N containing material on a first conductive surface of a substrate relative to a second, dielectric surface of the same substrate. In some aspects, methods of forming an Al and N containing protective layer or etch stop layer for use in integrated circuit fabrication are provided.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of U.S. application Ser. No.15/432,263, filed Feb. 14, 2017, which is a continuation-in-part of U.S.application Ser. No. 14/819,274, filed Aug. 5, 2015, which is related toU.S. Provisional Application No. 62/438,055, filed Dec. 22, 2016, eachof which is hereby incorporated by reference in its entirety.

BACKGROUND OF THE INVENTION Field of the Invention

The present application relates to selective deposition of aluminum andnitrogen containing material, for example an Al and N containing thinfilm on a first surface of a substrate relative to a second surface.

Description of the Related Art

Integrated circuits are currently manufactured by an elaborate processin which various layers of materials are sequentially constructed in apredetermined arrangement on a semiconductor substrate.

The predetermined arrangement of materials on a semiconductor substrateis often accomplished by deposition of a material over the entiresubstrate surface, followed by removal of the material frompredetermined areas of the substrate, such as by deposition of a masklayer and subsequent selective etching process.

In certain cases, the number of steps involved in manufacturing anintegrated surface on a substrate may be reduced by utilizing aselective deposition process, wherein a material is selectivelydeposited on a first surface relative to a second surface without theneed, or with reduced need for subsequent processing. Methods aredisclosed herein for selective deposition on a first surface ofsubstrate relative to a second, different surface of the substrate.

SUMMARY OF THE INVENTION

In some aspects, processes for selectively depositing a materialcomprising aluminum and nitrogen are provided. In some embodiments amaterial comprising aluminum and nitrogen is deposited on a firstsurface of a substrate relative to a second dielectric surface of thesame substrate in a process comprising one or more deposition cyclescomprising contacting the substrate with a first vapor phase precursorcomprising aluminum and contacting the substrate with a second vaporphase precursor comprising nitrogen. In some embodiments a materialcomprising aluminum and nitrogen is deposited on a first surface of asubstrate relative to a second Si—O surface of the same substrate in aprocess comprising one or more deposition cycles comprising contactingthe substrate with a first vapor phase precursor comprising aluminum andcontacting the substrate with a second vapor phase precursor comprisingnitrogen. In some embodiments a material comprising aluminum andnitrogen is deposited on a first surface of a substrate relative to asecond non-conductive surface of the same substrate in a processcomprising one or more deposition cycles comprising contacting thesubstrate with a first vapor phase precursor comprising aluminum andcontacting the substrate with a second vapor phase precursor comprisingnitrogen. In some embodiments the material comprising aluminum andnitrogen is deposited on the first surface of the substrate relative tothe second dielectric surface of the same substrate with a selectivelygreater than about 50%. In some embodiments the first surface comprisesat least one of: copper, titanium nitride, tungsten, and siliconnitride. In some embodiments the material comprising aluminum andnitrogen is an aluminum nitride thin film. In some embodiments thealuminum nitride thin film comprises oxygen.

In some embodiments the first vapor phase precursor comprising aluminumis an organometallic aluminum compound. In some embodiments the firstvapor phase precursor comprising aluminum does not comprise any metalsother than aluminum. In some embodiments the first vapor phase precursorcomprising aluminum has the formula R₃Al, wherein each R can beindependently selected from C₁-C₄ alkyl groups. In some embodiments thefirst vapor phase precursor comprising aluminum does not comprise ahalide. In some embodiments the first vapor phase precursor comprisingaluminum comprises one chlorine ligand and at two alkyl ligands. In someembodiments the first vapor phase precursor comprising aluminumcomprises at least one hydrogen ligand and at least one alkyl ligand. Insome embodiments the first vapor phase precursor comprising aluminumdoes not comprise nitrogen, silicon, or oxygen. In some embodiments thefirst vapor phase precursor comprising aluminum comprisestriethylaluminum (TEA), trimethylaluminum (TMA) or tritertbutylaluminum(TTBA) and the second vapor phase precursor comprising nitrogencomprises NH₃.

In some embodiments the second dielectric surface comprises Si—O bonds.In some embodiments the process comprises a thermal atomic layerdeposition (ALD) process. In some embodiments the process does notcomprise plasma in at least 2 consecutive deposition cycles. In someembodiments the process further comprises exposing the substrate to apretreatment reactant prior to a first deposition cycle. In someembodiments the pretreatment reactant comprises plasma. In someembodiments exposing the substrate to a pretreatment reactant prior to afirst deposition cycle enhances the selectivity by a factor of more thanabout 2. In some embodiments the process further comprises exposing thesubstrate to plasma after at least one deposition cycle. In someembodiments the substrate is exposed to plasma after more than 10deposition cycles.

In some embodiments the material comprising aluminum and nitrogen hasetch selectivity relative to SiO₂ in dilute HF. In some embodiments aratio of material comprising aluminum and nitrogen deposited on thefirst surface of the substrate relative to the second dielectric surfaceof the same substrate is greater than about 10:1, and wherein athickness of material comprising aluminum and nitrogen deposited onfirst surface of the substrate is greater than about 5 nm. In someembodiments a ratio of material comprising aluminum and nitrogendeposited on the first surface of the substrate relative to the seconddielectric surface of the same substrate is greater than about 10:1 andwherein a thickness of material comprising aluminum and nitrogendeposited on first surface of the substrate is greater than about 1 nm.In some embodiments a ratio of material comprising aluminum and nitrogendeposited on the first surface of the substrate relative to the seconddielectric surface of the same substrate is greater than about 10:1 andwherein the process comprises between about 1 and 25 deposition cycles.In some embodiments a ratio of material comprising aluminum and nitrogendeposited on the first surface of the substrate relative to the seconddielectric surface of the same substrate is greater than about 10:1, andwherein the process comprises between about 1 and 150 deposition cycles.In some embodiments less than about 0.1 nm of material comprisingaluminum and nitrogen is deposited on the second dielectric surface ofthe substrate after between about 1 and 25 deposition cycles. In someembodiments a ratio of a wet etch rate of the deposited aluminum andnitrogen containing material to a wet etch rate of SiO₂ is less thanabout 1:5.

In some embodiments the second dielectric surface of the substrateoverlies a source/drain region, and the process further comprisesremoving the second dielectric surface of the substrate to therebyexpose the source/drain region of the substrate, and forming a contactover the exposed source/drain region of the substrate.

In some aspects processes for selectively depositing AlN on a firstsurface of a substrate relative to a second dielectric surface of thesame substrate are provided. In some embodiments the process maycomprise one or more deposition cycles comprising alternately andsequentially contacting the substrate with vapor phasetritertbutylaluminum (TTBA) and vapor phase NH. In some embodiments theAlN is deposited on the first surface of the substrate relative to thesecond dielectric surface of the same substrate with a selectivitygreater than about 50%. In some embodiments the second dielectricsurface comprises Si—O bonds. In some embodiments the process comprisesa thermal atomic layer deposition (ALD) process. In some embodiments theprocess does not comprise plasma in at least 2 consecutive depositioncycles. In some embodiments the process further comprises exposing thesubstrate to a pretreatment reactant prior to a first deposition cycle.In some embodiments the pretreatment reactant comprises plasma. In someembodiments the process may include some or all of the features of anyother embodiment described herein above.

In some aspects processes for forming an etch stop layer in aself-aligned contact formation are provided. In some embodiments aprocess may comprise providing a semiconductor substrate comprising afirst surface and a second dielectric surface overlying a source/drainregion, removing a portion of the first surface of the substrate to forma recess therein, selectively depositing a material comprising aluminumand nitrogen on the first surface relative to the second dielectricsurface, removing the second dielectric surface of the substrate tothereby expose the source/drain region of the substrate, and forming acontact over the exposed source/drain region of the substrate. In someembodiments the first surface comprises at least one of: copper,titanium nitride, tungsten, and silicon nitride. In some embodiments thematerial comprising aluminum and nitrogen is an aluminum nitride thinfilm. In some embodiments the aluminum nitride thin film comprisesoxygen. In some embodiments the process may include some or all of thefeatures of any other embodiment described herein above.

According to some aspects, processes for selectively forming AlN on afirst surface relative to a second different surface are provided. Insome embodiments the process comprises one or more super-cyclescomprising selectively depositing AlN on a first surface relative to asecond different surface, etching the deposited AlN, wherein etching thedeposited AlN removes substantially all of the deposited AlN from thesecond surface of the substrate and does not remove substantially all ofthe AlN from the first surface of the substrate.

In some embodiments the super-cycle further comprises repeating theselectively depositing AlN and etching deposited AlN steps until an AlNthin film of a desired thickness has been formed on the first surface.In some embodiments the super-cycle further comprises exposing thesubstrate to a pretreatment reactant prior to selectively depositingAlN. In some embodiments the pretreatment reactant comprises plasma. Insome embodiments the plasma is generated from a gas comprising H₂.

In some embodiments selectively depositing AlN on a first surfacerelative to a second different surface comprises performing one or moreselective deposition sub-cycles comprising contacting the substrate witha first vapor phase precursor comprising aluminum, contacting thesubstrate with a second vapor phase precursor comprising nitrogen, andwherein the AlN is deposited on the first surface of the substraterelative to the second dielectric surface of the same substrate with aselectivity greater than about 5%. In some embodiments the selectivedeposition sub-cycle further comprising repeating the selectivedeposition sub-cycle until AlN of a desired thickness is deposited onthe first surface. In some embodiments selectively depositing AlNcomprises repeating the selective deposition sub-cycle until theselective deposition sub-cycle is no longer selective.

In some embodiments the first vapor phase precursor comprising aluminumcomprises one of tritertbutylaluminum (TTBA), trimethylaluminum (TMA) ortriethylaluminum (TEA). In some embodiments the second vapor phaseprecursor comprising nitrogen comprises NH₃.

In some embodiments etching the deposited AlN comprises an atomic layeretching (ALE) process comprising one or more etching sub-cyclescomprising contacting the substrate with a first vapor phase halide etchreactant, and contacting the substrate with a second vapor phase etchreactant comprising aluminum. In some embodiments the first vapor phasehalide etch reactant comprises NF₃ or NbF₅. In some embodiments thesecond vapor phase etch reactant comprising aluminum comprisestrimethylaluminum (TMA) or triethylaluminum (TEA). In some embodimentsthe etching sub-cycle is carried out at a process temperature of about300° C. In some embodiments the first surface comprises W and the secondsurface comprises SiO₂. In some embodiments the first surface comprisesTiN and the second surface comprises SiO₂. In some embodiments AlN isselectively formed on the first surface of the substrate relative to thesecond surface with a selectivity greater than about 99%.

In some embodiments selectively depositing AlN on a first surfacerelative to a second different surface comprises performing a selectivedeposition sub-cycle, wherein the selective deposition sub-cycle isrepeated from 1 to about 300 times, wherein etching the deposited AlNcomprises an atomic layer etching (ALE) process in which an etchsub-cycle is repeated from 1 to about 150 times.

In some embodiments a process for selectively forming AlN on a firstsurface of a substrate relative to a second different surface of thesame substrate comprises a super-cycle comprising a selective depositionsub-cyle comprising alternately and sequentially contacting thesubstrate with a first vapor phase precursor comprising aluminum and asecond vapor phase precursor comprising nitrogen such that AlN isdeposited on the first surface of the substrate relative to the seconddifferent surface of the same substrate with a selectivity greater thanabout 5%, and an atomic layer etch sub-cycle comprising alternately andsequentially contacting the substrate with a first vapor phase halideetch reactant and a second vapor phase etch reactant comprising aluminumsuch that the atomic layer etch step removes substantially all of thedeposited AlN from the second surface of the substrate and does notremove substantially all of the AlN from the first surface of thesubstrate.

In some embodiments the super-cycle is repeated one or more times. Insome embodiments the super-cycle further comprising exposing thesubstrate to a plasma generated from a gas comprising H₂ prior to theselective deposition step.

In some embodiments the first vapor phase precursor comprising aluminumcomprises TMA, the second vapor phase precursor comprising nitrogencomprises NH₃, the first vapor phase halide etch reactant comprises NF₃,and the second vapor phase etch reactant comprising aluminum comprisesTMA. In some embodiments the first surface is a conductive surface andthe second surface is a dielectric surface.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention will be better understood from the Detailed Descriptionand from the appended drawings, which are meant to illustrate and not tolimit the invention, and wherein:

FIG. 1 illustrates a deposition process flow for selectively depositingan Al and N containing material on a first surface of a substraterelative to a second, different surface of the same substrate;

FIG. 2 illustrates a deposition process flow for selectively depositingAlN on a first surface of a substrate relative to a second, differentsurface of the same substrate;

FIG. 3 illustrates a deposition process flow for selectively depositingan Al and N containing material on a first surface of a substraterelative to a second, different surface of the same substrate includinga selective deposition sub-cycle and an atomic layer etching sub-cycle;

FIG. 4 illustrates a process flow for forming self-aligned contactstructures;

FIG. 5 illustrates another process flow for forming self-aligned contactstructures;

FIG. 6 is a graph of deposited material thickness versus number ofdeposition cycles for Al and N containing material selectively depositedon a first TiN surface relative to a second SiO₂ surface;

FIG. 7 is a graph of deposited material thickness versus number ofdeposition cycles for Al and N containing material selectively depositedon a first TiN surface relative to a SiO₂ and native oxide secondsurfaces;

FIG. 8 is a graph of deposited material thickness versus number ofdeposition cycles for Al and N containing material selectively depositedon a first TiN surface relative to a second native oxide surface;

FIG. 9 is a graph of deposited material thickness versus number ofdeposition cycles for Al and N containing material selectively depositedon a first TiN or W surface relative to a second SiO₂ surface;

FIG. 10A is a scanning electron microscope (SEM) image of AlN that hasbeen selectively deposited on tungsten lines relative to SiO₂;

FIG. 10B is an enhanced view of a portion of the SEM image of FIG. 10A.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

In some situations it is desirable to selectively deposit a materialcomprising aluminum (Al) and nitrogen (N), such as aluminum nitride(AlN) on one surface of a substrate relative to a second, differentsurface of the same substrate. For example, selective deposition of anAl and N containing material may be used to form capping layers, barrierlayers, or etch stop layers, such as a contact etch stop layer. Forexample, an Al and N containing material may be deposited selectively ona first surface of a substrate preferentially over a second, differentsurface, such as a dielectric surface of the same substrate.

In some embodiments a substrate comprising a first surface and a second,different surface is provided and an Al and N containing material isselectively deposited on the first surface relative to the secondsurface using an ALD type process comprising a plurality of depositioncycles, each cycle comprising alternately and sequentially contacting asubstrate with a vapor phase first precursor and a vapor phase secondprecursor. In some embodiments the selectively deposited Al and Ncontaining material is AlN.

In some embodiments an aluminum and nitrogen containing material, suchas AlN, is selectively deposited on a metal surface of a substratecomprising both a conductive surface and a dielectric surface. In someembodiments, AlN is selectively deposited on a first conductive surfaceof a substrate, such as a Cu, W, or TiN surface relative to a seconddielectric surface, such as a SiO₂ or low-k surface of the samesubstrate. In some embodiments AlN is selectively deposited on a firstsurface that is not a conductive surface, such as a SiN surface,relative to a second dielectric surface, such as a SiO₂ or low-k surfaceof the same substrate. In some embodiments AlN is selectively depositedon a Cu surface, relative to a second, different surface. In someembodiments AlN is selectively deposited on a W surface, relative to asecond, different surface. In some embodiments AlN is selectivelydeposited on a TiN surface, relative to a second, different surface. Insome embodiments AlN is selectively deposited on a SiN surface, relativeto a second, different surface.

In some embodiments processes for selectively depositing aluminum andnitrogen containing material, such as AlN may comprise subjecting thesubstrate to an etch process after selectively depositing aluminum andnitrogen containing material on a first surface relative to a seconddifferent surface, wherein the etch process removes substantially all ofany deposited aluminum and nitrogen containing material from a secondsurface of a substrate and does not remove substantially all of thedeposited aluminum and nitrogen containing material from a first surfaceof the substrate. In some embodiments the etch process may be an atomiclayer etch process. In some embodiments the atomic layer etch processmay comprise alternately and sequentially contacting the substrate witha first vapor phase etch reactant comprising aluminum and a second vaporphase halide etch reactant.

In some embodiments processes for selectively depositing aluminum andnitrogen containing material, such as AlN, may comprising a plurality ofsuper-cycles comprising selectively depositing Al and N containingmaterial on the first surface of a substrate relative to the secondsurface of the substrate and etching the deposited Al and N containingmaterial such that substantially all of any deposited Al and Ncontaining material is removed from the second surface while at leastsome Al and N containing material remains on the first surface. Thisselective deposition super-cycle may optionally be repeated until adesired amount of Al an N containing material is deposited on the firstsurface of the substrate. In some embodiments substantially no aluminumand nitrogen containing material remains on the second surface aftereach selective deposition super-cycle. In some embodiments substantiallyno aluminum and nitrogen containing material remains on the secondsurface after the selective deposition process.

In some embodiments a selective deposition super-cycle may furthercomprise performing a pretreatment process before selectively depositingthe Al and N containing material. In some embodiments the pretreatmentprocess may comprise exposing the substrate to a pretreatment reactant.In some embodiments the pretreatment reactant may comprise a plasma, forexample a plasma generated from a gas comprising H₂.

ALD Type Processes

ALD type processes are based on controlled, self-limiting surfacereactions of precursor chemicals. Gas phase reactions are avoided byalternately and sequentially contacting the substrate with theprecursors. Vapor phase reactants are separated from each other on thesubstrate surface, for example, by removing excess reactants and/orreactant byproducts from the reaction chamber between reactant pulses.In some embodiments one or more substrate surfaces are alternately andsequentially contacted with two or more vapor phase precursors, orreactants. Contacting a substrate surface with a vapor-phase reactantmeans that the reactant vapor is in contact with the substrate surfacefor a limited period of time. In other words, it can be understood thatthe substrate surface is exposed to each vapor phase reactant for alimited period of time.

Briefly, a substrate comprising at least a first surface and second,different surface is heated to a suitable deposition temperature,generally at lowered pressure. Deposition temperatures are generallymaintained below the thermal decomposition temperature of the reactantsbut at a high enough level to avoid condensation of reactants and toprovide the activation energy for the desired surface reactions. Ofcourse, the appropriate temperature window for any given ALD reactionwill depend upon the surface termination and reactant species involved.Here, the temperature varies depending on the precursors being used andis preferably at or below about 500° C., preferably between about 250°C. and about 500° C., more preferably between about 275° C. and about450° C., more preferably between about 300° C. and about 425° C., andmost preferably between about 325° C. and about 400° C.

The surface of the substrate is contacted with a vapor phase firstreactant. In some embodiments a pulse of vapor phase first reactant isprovided to a reaction space containing the substrate. In someembodiments the substrate is moved to a reaction space containing vaporphase first reactant. Conditions are preferably selected such that nomore than about one monolayer of the first reactant is adsorbed on thesubstrate surface in a self-limiting manner. The appropriate contactingtimes can be readily determined by the skilled artisan based on theparticular circumstances. Excess first reactant and reaction byproducts,if any, are removed from the substrate surface, such as by purging withan inert gas or by removing the substrate from the presence of the firstreactant.

Purging means that vapor phase precursors and/or vapor phase byproductsare removed from the substrate surface such as by evacuating a chamberwith a vacuum pump and/or by replacing the gas inside a reactor with aninert gas such as argon or nitrogen. Typical purging times are fromabout 0.05 to 20 seconds, more preferably between about 1 and 10, andstill more preferably between about 1 and 2 seconds. However, otherpurge times can be utilized if necessary, such as where highly conformalstep coverage over extremely high aspect ratio structures or otherstructures with complex surface morphology is needed.

The surface of the substrate is contacted with a vapor phase secondgaseous reactant. In some embodiments a pulse of a second gaseousreactant is provided to a reaction space containing the substrate. Insome embodiments the substrate is moved to a reaction space containingthe vapor phase second reactant. Excess second reactant and gaseousbyproducts of the surface reaction, if any, are removed from thesubstrate surface. The steps of contacting and removing are repeateduntil a thin film of the desired thickness has been selectively formedon the first surface of substrate, with each cycle leaving no more thanabout a molecular monolayer. Additional phases comprising alternatelyand sequentially contacting the surface of a substrate with otherreactants can be included to form more complicated materials, such asternary materials.

As mentioned above, each phase of each cycle is preferablyself-limiting. An excess of reactant precursors is supplied in eachphase to saturate the susceptible structure surfaces. Surface saturationensures reactant occupation of all available reactive sites (subject,for example, to physical size or “steric hindrance” restraints) and thusensures excellent step coverage. Typically, less than one molecularlayer of material is deposited with each cycle, however, in someembodiments more than one molecular layer is deposited during the cycle.

Removing excess reactants can include evacuating some of the contents ofa reaction space and/or purging a reaction space with helium, nitrogenor another inert gas. In some embodiments purging can comprise turningoff the flow of the reactive gas while continuing to flow an inertcarrier gas to the reaction space.

The substrate can comprise various types of materials. Whenmanufacturing integrated circuits, the substrate typically comprises anumber of thin films with varying chemical and physical properties. Forexample and without limitation, the substrate may comprise a dielectriclayer and a metal layer. In some embodiments the substrate can comprisemetal carbide. In some embodiments the substrate can comprise aconductive oxide.

Preferably the substrate has a first surface comprising a conductivesurface, such as metal or metallic surface. In some embodiments thefirst surface comprises a metal nitride. In some embodiments the firstsurface comprises one or more transition metals. The transition metalcan be selected from the group: Ti, V, Cr, Mn, Nb, Mo, Ru, Rh, Pd, Ag,Au, Hf, Ta, W, Re, Os, Ir and Pt. In other embodiments the transitionmetal is selected from the group: Fe, Co, Ni. In some embodiments thefirst surface preferably comprises copper. In some embodiments the firstsurface comprises a noble metal. The noble metal can be selected fromthe group: Au, Pt, Ir, Pd, Os, Ag, Re, Rh, and Ru. In some preferredembodiments the first surface comprises at least one of Cu, W, TiN, TaN,or SiN.

In some embodiments the first surface may comprise more than onematerial, for example TiN and SiN.

In some embodiments the first surface comprises a metal silicide, suchas transition metal silicide. In some embodiments the first surfacecomprises a metallic film comprising a transition metal, such as atransition metal carbide or carbon-containing transition metal material.In some embodiments the first surface may comprise Al. In someembodiments the first surface comprises an alloy of metals or metallicmaterials.

The second surface is preferably a dielectric surface, such as SiO₂,GeO₂, or a low-k surface. In some embodiments, the dielectric comprisesSiO₂. In some embodiments the dielectric is a porous material. In someembodiments the porous dielectric contains pores which are connected toeach other, while in other embodiments the pores are not connected toeach other. In some embodiments the dielectric comprises a low-kmaterial, defined as an insulator with a dielectric value below about4.0. In some embodiments the dielectric value of the low-k material isbelow about 3.5, below about 3.0, below about 2.5 and below about 2.3.In some embodiments the second surface comprises Si—O bonds. In someembodiments the second surface is deactivated, for example by a plasmatreatment. In some embodiments the second surface is a non-conductingsurface. In some embodiments the second surface has a resistivitygreater than about 1 ohm.m. In some embodiments the second surfacecomprises Si—O bonds and has a resistivity less than about 1 ohm.m. Theterm dielectric is used herein for the sake of simplicity indistinguishing from the other, first surface, namely the metal ormetallic surface. Unless indicated otherwise with respect to particularembodiments, the term dielectric in the context of this application canbe understood to indicate all surfaces which have a very highresistivity.

The precursors employed in the ALD type processes may be solid, liquidor gaseous materials under standard conditions (room temperature andatmospheric pressure), provided that the precursors are in vapor phasebefore they are contacted with the substrate surface. Contacting asubstrate surface with a vaporized precursor means that the precursorvapor is in contact with the substrate surface for a limited period oftime. Typically, the contacting time is from about 0.05 to 10 seconds.However, depending on the substrate type and its surface area, thecontacting time may be even higher than 10 seconds. Contacting times canbe on the order of minutes in some cases. The optimum contacting timecan be determined by the skilled artisan based on the particularcircumstances.

The mass flow rate of the precursors can also be determined by theskilled artisan. In some embodiments the flow rate of metal precursorsis preferably between about 1 and 1000 sccm without limitation, morepreferably between about 100 and 500 sccm.

The pressure in a reaction chamber is typically from about 0.01 to about20 mbar, more preferably from about 1 to about 10 mbar. However, in somecases the pressure will be higher or lower than this range, as can bedetermined by the skilled artisan given the particular circumstances.

Before starting the deposition of the film, the substrate is typicallyheated to a suitable growth temperature. The growth temperature variesdepending on the type of thin film formed, physical properties of theprecursors, etc. The growth temperatures are discussed in greater detailbelow in reference to each type of thin film formed. The growthtemperature can be less than the crystallization temperature for thedeposited materials such that an amorphous thin film is formed or it canbe above the crystallization temperature such that a crystalline thinfilm is formed. The preferred deposition temperature may vary dependingon a number of factors such as, and without limitation, the reactantprecursors, the pressure, flow rate, the arrangement of the reactor,crystallization temperature of the deposited thin film, and thecomposition of the substrate including the nature of the material to bedeposited on. The specific growth temperature may be selected by theskilled artisan.

Reactors capable of being used to grow thin films can be used for thedeposition. Such reactors include ALD reactors, as well as CVD reactorsequipped with appropriate equipment and means for providing theprecursors. According to some embodiments, a showerhead reactor may beused.

Examples of suitable reactors that may be used include commerciallyavailable equipment such as the F-120® reactor, F-450® reactor, Pulsar®reactors—such as the Pulsar® 2000 and the Pulsar® 3000—EmerALD® reactorand Advance® 400 Series reactors, available from ASM America, Inc. ofPhoenix, Ariz. and ASM Europe B.V., Almere, Netherlands. Othercommercially available reactors include those from ASM Japan K.K (Tokyo,Japan) under the tradename Eagle® XP and XP8.

In some embodiments a batch reactor may be used. Suitable batch reactorsinclude, but are not limited to, reactors commercially available fromand ASM Europe B.V (Almere, Netherlands) under the trade names ALDA400™and A412™. In some embodiments a vertical batch reactor is utilized inwhich the boat rotates during processing, such as the A412™. Thus, insome embodiments the wafers rotate during processing. In someembodiments in which a batch reactor is used, wafer-to-wafer uniformityis less than 3% (lsigma), less than 2%, less than 1% or even less than0.5%.

The growth processes can optionally be carried out in a reactor orreaction space connected to a cluster tool. In a cluster tool, becauseeach reaction space is dedicated to one type of process, the temperatureof the reaction space in each module can be kept constant, whichimproves the throughput compared to a reactor in which the substrate isheated up to the process temperature before each run.

A stand-alone reactor can be equipped with a load-lock. In that case, itis not necessary to cool down the reaction space between each run.

Preferably, for forming an Al and N containing material, each ALD cyclecomprises at least two distinct phase. Contacting the substrate with afirst precursor and thereafter removing excess first precursor andreaction byproducts from the substrate surface may be considered a phaseand may be referred to as a first phase, first precursor phase, Alphase, Al precursor phase, first Al phase, and/or first Al precursorphase. For a deposition cycle, in a first phase, the substrate iscontacted with a first precursor comprising Al, which forms no more thanabout one monolayer on the substrate surface. In a second phase, thesubstrate is contacted with a second precursor comprising nitrogen andmay convert adsorbed first precursor to an Al and N containing material.Contacting the substrate with a second precursor and thereafter removingexcess second precursor and reaction byproducts from the substratesurface may be considered a phase and may be referred to as a secondphase, second precursor phase, N phase, N precursor phase, first Nphase, and/or first N precursor phase. One or more of the precursors maybe provided with the aid of a carrier gas, such as N₂, Ar, or He.Additional phases may be added and phases may be removed as desired toadjust the composition of the final film.

Referring to FIG. 1 and according to preferred embodiments an Al and Ncontaining material is selectively deposited on a first surface of asubstrate comprising a first surface and a second, different surface byan ALD type deposition process 100 comprising at least one cyclecomprising:

contacting the substrate with a first vapor phase precursor comprisingAl at step 120;

removing excess first precursor and reaction by products, if any, fromthe substrate at step 130;

contacting the substrate with a second vapor phase precursor comprisingnitrogen at step 140;

removing from the substrate, at step 150, excess second precursor andany gaseous by-products, and;

optionally repeating at step 160 the contacting and removing steps untilan Al and N containing material of the desired thickness has beenformed.

In some embodiments one or more surfaces of the substrate may besubjected to a pretreatment process prior to beginning the depositionprocess 100. In some embodiments a pretreatment process may enhance theselectivity of the selective deposition process 100. In some embodimentsa pretreatment process may enhance deposition of an Al and N containingmaterial on one surface relative to one or more different surfaces priorto beginning the deposition process 100. In some embodiments apretreatment process may inhibit deposition of an Al and N containingmaterial on one surface relative to one or more different surface priorto beginning the deposition process 100. In FIG. 1 this is indicated bystep 110 in which the substrate can be exposed to a pretreatmentreactant, for example a plasma, prior to deposition of an Al and Ncontaining material.

In some embodiments a pretreatment process may comprise exposing thesubstrate to a pretreatment reactant. In some embodiments a pretreatmentreactant may comprise oxygen. In some embodiments the pretreatmentreactant comprises oxygen radicals, atomic oxygen, oxygen plasma, orcombinations thereof. In some embodiments a pretreatment reactant maycomprise nitrogen. In some embodiments the pretreatment reactantcomprises nitrogen radicals, atomic nitrogen, nitrogen plasma, orcombinations thereof. In some embodiments a pretreatment reactant maycomprise hydrogen. In some embodiments the pretreatment reactantcomprises hydrogen radicals, atomic hydrogen, hydrogen plasma, orcombinations thereof.

In some embodiments utilizing a pretreatment process wherein thesubstrate is exposed to a pretreatment reactant comprising oxygenplasma, O₂ may be provided, for example, from about 1 to about 2000sccm, more preferably from about 5 to about 1000 sccm, and mostpreferably from about 50 to about 500 sccm. In some embodiments O₂ maybe provide at about 300 sccm. In some embodiments utilizing apretreatment process wherein the substrate is exposed to a pretreatmentreactant comprising nitrogen plasma, N₂ may be provided, for example, atabout from about 1 to about 5000 sccm, more preferably from about 5 toabout 2000 sccm, and most preferably from about 50 to about 500 sccm. Insome embodiments N₂ may be provided at about 300 sccm. In someembodiments a pretreatment process wherein the substrate is exposed to apretreatment reactant comprising hydrogen plasma, H₂ may be provided,for example, from about 1 to about 2000 sccm, more preferably from about5 to about 1000 sccm, and most preferably from about 10 to about 100sccm. In some embodiments H₂ may be provided at about 50 sccm. Similarconditions can be used for other types of plasma.

In some embodiments a pretreatment process may comprise exposing thesubstrate to a pretreatment reactant at a pretreatment temperature. Insome embodiments the pretreatment temperature may be great than about20° C. In some embodiments a pretreatment temperature may be betweenabout 20° C. and about 500° C., more preferably between about 50° C. andabout 450° C., more preferably between about 150° C. and about 400° C.In some embodiments the pretreatment temperature may be about the sameas the deposition temperature. In some embodiments the pretreatmenttemperature may be different than the deposition temperature. In someembodiments plasma may be generated at a power of less than about 2500Watts, for example about 1 to about 1000 Watts, about 1 to about 500 W,or about 1 to about 200 W or less. In some embodiments plasma may begenerated at a power of 50 W. In some embodiments plasma may begenerated at a power of 100 W.

In some embodiments the plasma is provided for less than about 200seconds, for example about 180 seconds or less, about 60 seconds orless, about 30 seconds or less, about 10 seconds or less, or about 3seconds or less.

In some embodiments, plasma is formed in a reactor. In some embodiments,the plasma may be formed in situ on top of the substrate or in closeproximity to the substrate. In other embodiments, the plasma is formedupstream of the reaction chamber in a remote plasma generator and plasmaproducts are directed to the reaction chamber to contact the substrate.As will be appreciated by the skilled artisan, in the case of remoteplasma, the pathway to the substrate can be optimized to maximizeelectrically neutral species and minimize ion survival before reachingthe substrate.

In some embodiments the treated substrate is not exposed to the ambientenvironment after a pretreatment process and before beginning aselective deposition process. In some embodiments the treated substrateis not exposed to air after a pretreatment process and before beginninga selective deposition process.

In some embodiments a pretreatment process may be used to enhance theselectivity of the subsequent selective deposition process. In someembodiments a pretreatment process may enhance selective deposition ofan Al and N containing material on a first surface relative to a seconddifferent surface. In some embodiments a pretreatment process mayenhance the selectivity of a subsequent selective deposition process bya factor of more than about 2, more than about 5, or more than about 10.

In some embodiments a pretreatment process may be performed in the samereaction chamber or reactor as the subsequent deposition process 100. Insome embodiments a pretreatment process may be performed in a differentreaction chamber or reactor than the subsequent deposition process 100.

Referring again to FIG. 1, the substrate is contacted with a firstprecursor comprising Al at step 120. In some embodiments the firstprecursor is conducted into a reaction chamber in the form of vaporphase pulse and contacted with the surface of the substrate. Conditionsare preferably selected such that no more than about one monolayer ofthe precursor is adsorbed on the substrate surface in a self-limitingmanner. However, in some embodiments conditions may be selected suchthat more than one monolayer of the precursor may be formed.

The first precursor pulse is preferably supplied in gaseous form. Thefirst precursor gas is considered “volatile” for purposes of the presentdescription if the species exhibits sufficient vapor pressure under theprocess conditions to transport the species to the workpiece insufficient concentration to saturate exposed surfaces.

In some embodiments the first precursor contacts the substrate for about0.01 seconds to about 60 seconds, for about 0.02 seconds to about 30seconds, for about 0.025 seconds to about 20 seconds, for about 0.05seconds to about 5.0 seconds, about 0.05 seconds to about 2.0 seconds orabout 0.1 seconds to about 1.0 second.

The first precursor employed in the ALD type processes may be solid,liquid, or gaseous material under standard conditions (room temperatureand atmospheric pressure), provided that the first precursor is in vaporphase before it is conducted into the reaction chamber and contactedwith the substrate surface.

At step 130 excess first precursor and reaction byproducts, if any, areremoved from the substrate surface, for example by purging with a pulseof inert gas such as nitrogen or argon. Purging the reaction chambermeans that vapor phase precursors and/or vapor phase byproducts areremoved from the reaction chamber such as by evacuating the chamber witha vacuum pump and/or by replacing the gas inside the reactor with aninert gas such as argon or nitrogen. Typical purging times are fromabout 0.05 to 20 seconds, more preferably between about 1 and 10seconds, and still more preferably between about 1 and 2 seconds.However, other purge times can be utilized if necessary, such as whendepositing layers over extremely high aspect ratio structures or otherstructures with complex surface morphology is needed. The appropriatepurging times can be readily determined by the skilled artisan based onthe particular circumstances.

In other embodiments however, removing excess first precursor andreaction byproducts, if any, may comprise moving the substrate so thatthe first precursor no longer contacts the substrate. In someembodiments no precursor may be removed from the various parts of achamber. In some embodiments the substrate is moved from a part of thechamber containing a first precursor to another part of the chambercontaining a second precursor or no precursor at all. In someembodiments the substrate is moved from a first reaction chamber to asecond, different reaction chamber.

At step 140 the substrate is contacted with a second vapor phaseprecursor comprising N. In some embodiments the second precursor ispulsed into the chamber where it reacts with the first precursor boundto the first surface of the substrate. The reaction typically forms upto about a monolayer of an Al and N containing material on thesubstrate. In some embodiments, however, more than one molecular layerof an Al and N containing material is formed on the substrate.

In some embodiments, the second precursor may include nitrogen plasma ornitrogen radicals. In such embodiments, nitrogen may be energized withinthe reaction chamber or upstream of the reaction chamber. Where a plasmais desired, the flow of un-energized second precursor may comprise atype of purge gas, such that after the substrate has been exposed to anitrogen plasma for a desired period of time, the plasma generator maybe turned off and the flow of nitrogen precursor itself is used to clearthe reaction chamber of excess nitrogen plasma and unreacted byproducts.

While one skilled in the art will recognize that any number of suitablesecond precursors may be used, appropriate second precursors includenitrogen containing compounds that favorably react with the ligands of apreviously or subsequently deposited first precursor. Accordingly,selection of an appropriate second precursor may depend on the specificfirst precursor used and the nature of the ligands in the firstprecursor

In some embodiments the second precursor contacts the substrate forabout 0.01 seconds to about 60 seconds, for about 0.02 seconds to about30 seconds, for about 0.025 seconds to about 20 seconds, for about 0.05seconds to about 5.0 seconds, about 0.05 seconds to about 2.0 seconds orabout 0.1 seconds to about 1.0 second. However, depending on the reactortype, substrate type and its surface area, the second precursorcontacting time may be even higher than 10 seconds. In some embodiments,contacting times can be on the order of minutes. The optimum contactingtime can be readily determined by the skilled artisan based on theparticular circumstances.

The concentration of the second precursor in the reaction chamber may befrom about 0.01% by volume to about 99.0% by volume. And the secondprecursor may flow through the reaction chamber at a rate of betweenabout 1 standard cm³/min and about 4000 standard cm³/min.

At step 150, excess second precursor and gaseous by-products of thesurface reaction, if any, are removed from the substrate, as describedabove for step 130. In some embodiments excess precursor and reactionbyproducts are preferably removed with the aid of an inert gas.

The steps of contacting and removing may be optionally repeated at step160 until an Al and N containing material of a desired thickness hasbeen formed on the first surface of the substrate, with each cycleleaving no more than about a molecular monolayer. In some cases, itmight be desirable to achieve at least partial decomposition of at leastone the various precursors. Thus, in some embodiments conditions may beselected such that more than one molecular layer of an Al and Ncontaining material is formed on the substrate in each deposition cycle.

The Al and N containing material ALD processes of the present disclosuremay comprise one or more cycles. Some embodiments involve the repetitionof at least about 5 cycles, at least about 10 cycles, or at least about50 cycles. In some embodiments, no more than 100 cycles are performed toform a thin film of a desirable thickness.

In some embodiments the substrate surface and/or Al and N containingmaterial may optionally be subjected to a plasma treatment process. InFIG. 1 this is indicated by step 170. In some embodiments the plasmatreatment process may be performed after more than one deposition cyclehas been performed. In some embodiments a plasma treatment process maybe performed before the deposited Al and N containing material film iscontinuous or closed. In some embodiments a plasma treatment process maybe performed after about every 10 deposition cycles, after about every20 deposition cycles, or after about every 50 deposition cycles. In someembodiments at least 2 consecutive deposition cycles are performedwithout a plasma treatment process. In some embodiments at least 5 or 10deposition cycles are performed without a plasma treatment process. Insome embodiments a plasma treatment process may be performed before anydeposition been carried out; that is, before any deposition cycle isperformed.

In some embodiments a plasma treatment process may be performed in thesame reaction chamber or reactor as the deposition process 100. In someembodiments a plasma treatment process may be performed in a differentreaction chamber or reactor than the deposition process 100.

In some embodiments, plasma is formed in a reactor. In some embodiments,the plasma may be formed in situ on top of the substrate or in closeproximity to the substrate. In other embodiments, the plasma is formedupstream of the reaction chamber in a remote plasma generator and plasmaproducts are directed to the reaction chamber to contact the substrate.As will be appreciated by the skilled artisan, in the case of remoteplasma, the pathway to the substrate can be optimized to maximizeelectrically neutral species and minimize ion survival before reachingthe substrate.

In some embodiments, the Al and N containing material can be depositedusing a plurality of deposition cycles, and the plasma treatment can beapplied at one or more times, including, for example, before deposition,after every deposition cycle, at pre-determined intervals duringdeposition, or after an Al and N containing material of desiredthickness is deposited.

In some embodiments a plasma treatment process comprises exposing thesubstrate to direct plasma. In some embodiments a plasma treatmentprocess comprises exposing the substrate to remote plasma. In someembodiments a plasma treatment process comprises exposing the substrateto excited species or atomic species created in plasma discharge butdoes not comprise a substantial amount, if any, of ions. In someembodiments the plasma may comprise oxygen. In some embodiments theplasma may comprise nitrogen. Although referred to as a plasma treatmentprocess, in some embodiments a reactive oxygen species that does notcomprise plasma may be used, for example ozone. In some embodiments theplasma may comprise hydrogen.

In some embodiments utilizing a pretreatment process or plasma treatmentprocess the substrate is exposed to a reactant comprising oxygen plasma.O₂ may be provided as a source gas, for example, from about 1 to about2000 sccm, more preferably from about 5 to about 1000 sccm, and mostpreferably from about 50 to about 500 sccm. In some embodiments O₂ maybe provide at about 300 sccm.

In some embodiments utilizing a pretreatment process or plasma treatmentprocess the substrate is exposed to a reactant comprising nitrogenplasma. N₂ may be provided as a source gas, for example, at about fromabout 1 to about 5000 sccm, more preferably from about 5 to about 2000sccm, and most preferably from about 50 to about 500 sccm. In someembodiments N₂ may be provided at about 300 sccm.

In some embodiments utilizing a pretreatment process or plasma treatmentprocess the substrate is exposed to a reactant comprising hydrogenplasma. In some embodiments, H₂ may be provided as a source gas, forexample, from about 1 to about 2000 sccm, more preferably from about 5to about 1000 sccm, and most preferably from about 10 to about 100 sccm.In some embodiments H₂ may be provided at about 50 sccm. Similarconditions can be used for other types of plasma.

In some embodiments a plasma treatment process may comprise exposing thesubstrate to a reactant at a treatment temperature. In some embodimentsthe treatment temperature may be great than about 20° C. In someembodiments a treatment temperature may be between about 20° C. andabout 500° C., more preferably between about 50° C. and about 450° C.,more preferably between about 150° C. and about 400° C. In someembodiments the treatment temperature may be about the same as thedeposition temperature and/or the pretreatment temperature. In someembodiments the treatment temperature may be different than thedeposition temperature and/or pretreatment temperature.

In some embodiments plasma may be generated at a power of less thanabout 2500 Watts, for example about 1 to about 1000 Watts, about 1 toabout 500 W, or about 1 to about 200W or less. In some embodimentsplasma may be generated at a power of 50 W. In some embodiments plasmamay be generated at a power of 100 W.

In some embodiments the plasma is provided for less than about 200seconds, for example about 180 seconds or less, about 60 seconds orless, about 30 seconds or less, about 10 seconds or less, or about 3seconds or less.

In some embodiments a plasma treatment process 170 may be substantiallyidentical to a pretreatment process 110.

Although the illustrated Al and N containing material deposition cyclebegins with contacting the surface of the substrate with the first vaporphase precursor comprising Al, in other embodiments the deposition cyclebegins with contacting the surface of the substrate with the secondvapor phase precursor comprising nitrogen. It will be understood by theskilled artisan that contacting the substrate surface with the firstvapor phase precursor comprising Al and second vapor phase precursorcomprising nitrogen are interchangeable in the deposition cycle.

In some embodiments the substrate is moved such that different reactantsalternately and sequentially contact the surface of the substrate in adesired sequence for a desired time. In some embodiments the removingsteps, 130 and 150 are not performed. In some embodiments no reactantmay be removed from the various parts of a chamber. In some embodimentsthe substrate is moved from a part of the chamber containing a firstprecursor to another part of the chamber containing the second reactant.In some embodiments the substrate is moved from a first reaction chamberto a second, different reaction chamber.

The skilled artisan can determine the optimal reactant evaporationtemperatures based on the properties of the selected precursors. Theskilled artisan can determine the optimal reactant contact times throughroutine experimentation based on the properties of the selectedprecursors and the desired properties of the deposited Al and Ncontaining material.

The growth rate of the Al and N containing materials will vary dependingon the reaction conditions. As described below, in initial experiments,the growth rate varied between about 0.01 and about 2.0 Å/cycle. In someembodiments the growth rate may be from about 0.01 Å/cycle to about 3.0Å/cycle, preferably from about 0.1 Å/cycle to about 2.5 A/cycle, morepreferably 0.3 Å/cycle to about 2.0 Å/cycle.

In some embodiments the deposited Al and N containing material comprisesa thin film. In some embodiments the deposited Al and N containingmaterial comprises AlN, and in some embodiments the deposited Al and Ncontaining material is AlN. In some embodiments Al and N containingmaterials are formed that consist essentially of Al and N. In someembodiments, additional reactants may be used to incorporate into orcontribute other materials to the film, for example oxygen to formaluminum oxynitrides. In some embodiments where additional non-metalelements in addition to nitrogen are desired, an ALD process for formingthe Al and N containing material may comprise phases in addition to theinitial Al and N phases. For example, they may include an oxidationphase where metal aluminum oxynitrides are desired. In an oxidationphase, oxygen or an oxygen-containing precursor is provided in thereaction chamber and allowed to contact the substrate surface. Theoxygen phase may be part of one or more deposition cycles. In someembodiments a second metal phase may be provided in one or moredeposition cycles. The oxidation phase, or other desirable phase, mayfollow the Al phase or the N phase, but in either situation, it isdesirable in some embodiments, to remove excess oxygen (or otherreactant) and any reaction by-products from the reaction space beforeproceeding to the next phase. In some embodiments an additional phase,such as an oxygen, or additional metal phase may be provided after thefinal deposition cycle, or intermittently in the deposition process.

In some embodiments deposition of an Al and N containing material on afirst surface of a substrate relative to a second surface of thesubstrate is at least about 90% selective, at least about 95% selective,at least about 96%, 97%, 98% or 99% or greater selective. In someembodiments deposition of an Al and N containing material only occurs onthe first surface and does not occur on the second surface. In someembodiments deposition on the first surface of the substrate relative tothe second surface of the substrate is at least about 80% selective,which may be selective enough for some particular applications. In someembodiments the deposition on the first surface of the substraterelative to the second surface of the substrate is at least about 50%selective, which may be selective enough for some particularapplications. In some embodiments the deposition on the first surface ofthe substrate relative to the second surface of the substrate is atleast about 1%, at least about 2.5%, at least about 5%, at least about10%, at least about 15%, at least about 20%, at least about 25%, atleast about 30%, or at least about 40%, all of which may be selectiveenough for some particular applications.

In some embodiments the ratio of Al and N containing material depositedon a first surface of a substrate relative to a second surface of thesubstrate may be greater than or equal to about 10:1, greater than orequal to about 20:1, or greater than or equal to about 40:1. In someembodiments the ratio of Al and N containing material deposited on afirst surface of a substrate relative to a second surface of thesubstrate may be greater than or equal to about 10:1, greater than orequal to about 20:1, or greater than or equal to about 40:1 when thethickness of Al and N containing material deposited on the first surfaceis more than about 5 nm. In some embodiments the ratio of Al and Ncontaining material deposited on a first surface of a substrate relativeto a second surface of the substrate may be greater than or equal toabout 10:1, greater than or equal to about 20:1, or greater than orequal to about 40:1 when the thickness of Al and N containing materialdeposited on the first surface is more than about 2.5 nm. In someembodiments the ratio of Al and N containing material deposited on afirst surface of a substrate relative to a second surface of thesubstrate may be greater than or equal to about 10:1, greater than orequal to about 20:1, or greater than or equal to about 40:1 when thethickness of Al and N containing material deposited on the first surfaceis more than about 1 nm.

In some embodiments the ratio of Al and N containing material depositedon a first surface of a substrate relative to a second surface of thesubstrate may be greater than or equal to about 10:1, greater than orequal to about 20:1, or greater than or equal to about 40:1 when the Aland N containing material deposition process comprises between about 0and about 25 deposition cycles, between about 0 and about 50 depositioncycles, between about 0 and about 100 deposition cycles, or betweenabout 0 and about 150 deposition cycles. In some embodiments less thanabout 0.1 nm of Al and N containing material is deposited on the secondsurface of the substrate when an Al and N containing material depositionprocess comprises between about 0 and about 25 deposition cycles,between about 0 and about 50 deposition cycles, between about 0 andabout 100 deposition cycles, or between about 0 and about 150 depositioncycles.

In some embodiments an Al and N containing material has etch selectivityrelative to SiO₂, that is an Al and N containing material has an etchrate less than an etch rate of SiO₂, for example in dilute HF. In someembodiments an Al and N containing material has a wet etch rate (WER) ofless than ⅕ the thermal oxide removal rate of about 2-3 nm per minutewith diluted HF (0.5%). In some embodiments the wet etch rate of the Aland N containing material relative to the wet etch rate of thermallyoxidized silicon (SiO₂, TOX) is less than about 0.2 in 0.5% dHF. In someembodiments the wet etch rate of the Al and N containing materialrelative to the wet etch rate of TOX is less than about 0.1 in 0.5% dHF.In some embodiments the wet etch rate of the Al and N containingmaterial relative to the wet etch rate of TOX is less than about 0.05 in0.5% dHF.

Referring now to FIG. 2, in some embodiments a substrate comprising afirst surface and a second dielectric surface is provided and AlN isselectively deposited on the first surface of the substrate by acyclical deposition process 200 comprising at least one cyclecomprising:

contacting the substrate with vapor phase trimethylaluminum (TMA) atstep 220;

removing excess TMA and reaction by products, if any, from the surfaceat step 230;

contacting the substrate with vapor phase NH₃ at step 240;

removing from the surface excess NH₃ and any by-products at step 250,and;

optionally repeating at step 260 the contacting and removing steps untilan AlN thin film of the desired thickness has been formed.

Although the illustrated AlN deposition cycle begins with contacting thesubstrate with TMA, in other embodiments the deposition cycle beginswith contacting the substrate with NH₃. It will be understood by theskilled artisan that contacting the substrate surface with TMA and NH₃are interchangeable in the deposition cycle.

In some embodiments one or more surfaces of the substrate may besubjected to a pretreatment process prior to beginning the depositionprocess. In some embodiments a pretreatment process may enhance theselectivity of the selective deposition process 200. In some embodimentsa pretreatment process may enhance deposition of AlN on one surfacerelative to one or more different surfaces prior to beginning thedeposition process. In some embodiments a pretreatment process mayinhibit the deposition of AlN on one surface relative to one or moredifferent surface prior to beginning the deposition process. In FIG. 2this is indicated by step 210 in which the substrate can be exposed to apretreatment reactant, for example a plasma, prior to deposition of theAl and N containing material.

In some embodiments the substrate surface and/or AlN thin film mayoptionally be subjected to a plasma treatment process. In FIG. 2 this isindicated by step 270. In some embodiments this plasma treatment processmay be substantially the same as the plasma treatment process 170described above with respect to FIG. 1. In some embodiments the plasmatreatment process 270 may be substantially identical to the pretreatmentstep 210. In some embodiments the plasma treatment process may beperformed after more than one deposition cycle has been performed. Insome embodiments a plasma treatment process may be performed before thedeposited AlN film is continuous or closed. In some embodiments a plasmatreatment process may be performed after more than about 10 depositioncycles, after more than about 20 deposition cycles, or after more thanabout 50 deposition cycles. In some embodiments a plasma treatmentprocess may be performed in the same reaction chamber or reactor as thedeposition process 200. In some embodiments a plasma treatment processmay be performed in a different reaction chamber or reactor than thedeposition process 200.

In some embodiments a substrate comprising a first surface and a seconddielectric surface is provided and an Al and N containing material isselectively deposited on the first surface of the substrate by acyclical deposition process comprising at least one cycle comprisingalternately and sequentially contacting the substrate with a vapor phasefirst precursor and a vapor phase second precursor. In some embodimentsthe first precursor may comprise Al and the second precursor maycomprise N. In some embodiments the first precursor may comprisetritertbutylaluminum and the second precursor may comprise NH₃.

In some embodiments a substrate comprising a first surface and a seconddielectric surface is provided and AlN is selectively deposited on thefirst surface of the substrate by a cyclical deposition processcomprising at least one cycle comprising alternately and sequentiallycontacting the substrate with a vapor phase first precursor and a vaporphase second precursor. In some embodiments the first precursor maycomprise Al and the second precursor may comprise N. In some embodimentsthe first precursor may comprise tritertbutylaluminum and the secondprecursor may comprise NH₃.

In some embodiments a substrate is provided and AlN is deposited on atleast part of the substrate by a cyclical deposition process comprisingat least one cycle comprising alternately and sequentially contactingthe substrate with a vapor phase first precursor and a vapor phasesecond precursor and the first precursor may comprisetritertbutylaluminum and the second precursor may comprise NH₃.

In some embodiments, prior to deposition the substrate may be subjectedto a pretreatment process. In some embodiments a pretreatment processmay enhance the selectivity of the selective deposition process. In someembodiments a pretreatment process may enhance deposition of AlN on onesurface relative to one or more different surfaces prior to beginningthe deposition process. In some embodiments a pretreatment process mayinhibit deposition of AlN on one surface relative to one or moredifferent surface prior to beginning the deposition process. In someembodiments a pretreatment process may comprise exposing the substrateto a pretreatment reactant, for example plasma, prior to deposition ofAlN.

In some embodiments the substrate surface and/or AlN thin film mayoptionally be subjected to a plasma treatment process. In someembodiments this plasma treatment process may be substantially the sameas the plasma treatment processes 170 and 270 described above withrespect to FIG. 1 and FIG. 2. In some embodiments the plasma treatmentprocess may be substantially identical to the pretreatment process. Insome embodiments the plasma treatment process may be performed aftermore than one deposition cycle has been performed. In some embodiments aplasma treatment process may be performed before the deposited AlN filmis continuous or closed. In some embodiments a plasma treatment processmay be performed after less than about 10 deposition cycles, after lessthan about 20 deposition cycles, or after less than about 50 depositioncycles. In some embodiments a plasma treatment process may be performedin the same reaction chamber or reactor as the deposition process. Insome embodiments a plasma treatment process may be performed in adifferent reaction chamber or reactor than the deposition process.

Referring to FIG. 3 and according to some embodiments, an Al and Ncontaining material is selectively formed on a first surface relative toa second different surface of a substrate, the substrate comprising thefirst surface and the second, different surface by a process 300comprising at least one super-cycle 301 comprising:

selectively depositing the Al and N containing material on the firstsurface of the substrate relative to the second, different surface atstep 320;

etching the deposited Al and N containing material such thatsubstantially all of the deposited Al and N containing material isremoved from the second surface and not all of the deposited Al and Ncontaining material is removed from the first surface at step 330;

optionally repeating at step 340 the selectively depositing and etchingsteps until an Al and N containing material of the desired thickness hasbeen formed on the first surface of the substrate relative to the seconddifferent surface.

In some embodiments one or more surfaces of the substrate may besubjected to a pretreatment process at the beginning of the super-cycle301. In some embodiments a pretreatment process may enhance theselectivity of the selective deposition process step 320. In someembodiments a pretreatment process may enhance deposition of an Al and Ncontaining material on one surface relative to one or more differentsurfaces prior to a selective deposition step 320. In some embodiments apretreatment process may inhibit deposition of an Al and N containingmaterial on one surface relative to one or more different surfaces priorto a selective deposition step 320. In FIG. 3 this is indicated by step310 of super-cycle 301, in which the substrate can be exposed to apretreatment reactant, for example a plasma, prior to the selectivedeposition of an Al and N containing material at step 320.

In some embodiments a pretreatment process may be the same aspretreatment processes 110 and/or 210 as described herein with respectto FIGS. 1 and 2. In some embodiments a pretreatment process maycomprise exposing the substrate to a pretreatment reactant. In someembodiments a pretreatment reactant may comprise hydrogen. In someembodiments the pretreatment reactant comprises hydrogen radicals,atomic hydrogen, hydrogen plasma, or combinations thereof. In someembodiments the pretreatment reactant may comprise a plasma generatedfrom a gas comprising H₂.

In some embodiments, plasma is formed in a reactor. In some embodiments,the plasma may be formed in situ on top of the substrate or in closeproximity to the substrate. In other embodiments, the plasma is formedupstream of the reaction chamber in a remote plasma generator and plasmaproducts are directed to the reaction chamber to contact the substrate.As will be appreciated by the skilled artisan, in the case of remoteplasma, the pathway to the substrate can be optimized to maximizeelectrically neutral species and minimize ion survival before reachingthe substrate.

In some embodiments the treated substrate is not exposed to the ambientenvironment after a pretreatment process 310 and before beginning aselective deposition step 320. In some embodiments the treated substrateis not exposed to air after a pretreatment process 310 and beforebeginning a selective deposition process at step 320.

In some embodiments a pretreatment process may be used to enhance theselectivity of the subsequent selective deposition process. In someembodiments a pretreatment process may enhance selective deposition ofan Al and N containing material on a first surface relative to a seconddifferent surface, for example a first and second surface as describedherein. In some embodiments a pretreatment process may enhance theselectivity of a subsequent selective deposition process by a factor ofmore than about 2, more than about 5, or more than about 10.

In some embodiments a pretreatment process 310 may be performed in thesame reaction chamber or reactor as the subsequent selective depositionstep 320. In some embodiments a pretreatment process 310 may beperformed in a different reaction chamber or reactor than the subsequentselective deposition step 320.

Referring again to FIG. 3, Al and N containing material is selectivelydeposited on the first surface of the substrate relative to the secondsurface at step 320. In some embodiments selectively depositing the Aland N containing material at step 320 may comprise a selectivedeposition process comprising one or more deposition sub-cyclescomprising alternately and sequentially contacting the substrate with afirst vapor phase aluminum precursor and a second vapor phase nitrogenprecursor. In some embodiments the deposition sub-cycle may be repeatedbetween 1 and 1000 times, between 1 and 500 times, between 1 and 300times, between 1 and 200 times, between 1 and 50 times, between 1 and100 times, or between 1 and 50 times.

In some embodiments selectively depositing the Al and N containingmaterial at step 320 may comprise a selective deposition process asdescribed herein, for example with respect to FIGS. 1 and 2. In someembodiments selectively depositing the Al and N containing material atstep 320 may comprise an ALD type deposition process comprising at leastone sub-cycle comprising:

contacting the substrate with a first vapor phase precursor comprisingAl;

removing excess first precursor and reaction by products, if any, fromthe substrate;

contacting the substrate with a second vapor phase precursor comprisingnitrogen;

removing from the substrate, excess second precursor and any gaseousby-products, and;

optionally repeating at the contacting and removing steps until an Aland N containing material of the desired thickness has been formed.

In some embodiments selectively depositing the Al and N containingmaterial at step 320 may comprise an ALD type deposition processcomprising at least one sub-cycle comprising:

contacting the substrate with a first vapor phase precursor comprisingtrimethylaluminum (TMA);

removing excess first precursor and reaction by products, if any, fromthe substrate;

contacting the substrate with a second vapor phase precursor comprisingNH₃;

removing from the substrate, excess second precursor and any gaseousby-products, and;

optionally repeating at the contacting and removing steps until an Aland N containing material of the desired thickness has been formed

In some embodiments selectively depositing the Al and N containingmaterial at step 320 may comprise one or more deposition sub-cycles.Some embodiments involve the repetition of at least about 5 sub-cycles,at least about 10 sub-cycles, at least about 50 sub-cycles, at leastabout 100 sub-cycles, at least about 150 sub-cycles, at least about 200sub-cycles, at least about 300 sub-cycles, at least about 500sub-cycles, or at least about 1000 sub-cycles. In some embodiments aselective deposition sub-cycles may be repeated until the selectivedeposition sub-cycle is no longer selective. In some embodiments aselective deposition sub-cycles may be repeated until the selectivedeposition sub-cycle is no longer significantly selective. In someembodiments a selective deposition sub-cycles may be repeated until theselective deposition sub-cycle has lost a significant amount ofselectivity. In some embodiments a selective deposition sub-cycles maybe repeated until the selective deposition sub-cycle no longer achievesa desired level of selectivity, for example until the selectivedeposition sub-cycle no longer achieves about 50% selectivity, about 40%selectivity, about 30% selectivity, about 20% selectivity, about 10%selectivity, about 5% selectivity, about 2% selectivity, about 1%selectivity or less. That is, in some embodiments selectively depositingthe Al and N containing material at step 320 may comprise repeating aselective deposition sub-cycle, for example an ALD deposition cycle asdescribed herein until said sub-cycle no longer selectively deposited Aland N containing material on the first surface of the substrate relativeto the second surface. In some embodiments selectively depositing the Aland N containing material at step 320 may comprise repeating a selectivedeposition sub-cycle, for example an ALD deposition cycle as describedherein until the selectivity of said sub-cycle drops below apredetermined selectivity. For example, in some embodiments selectivelydepositing the Al and N containing material at step 320 may compriserepeating a selective deposition sub-cycle until said selectivedeposition sub-cycle has a selectivity less than about 50%, less thanabout 25%, less than about 15%, less than about 10%, less than about 5%,less than about 2%, less that about 1%, or lower.

Subsequent to selectively depositing the Al and N containing material atstep 320, the deposited Al and N containing material is etched, forexample by subjecting the Al and N containing material to an etchprocess at step 330. In some embodiments the etch process removessubstantially all of any deposited Al and N containing material from thesecond surface of the substrate and does not remove substantially all ofthe deposited Al and N containing material from the first surface of thesubstrate. In some embodiments the etch process may remove the same, ora similar amount or thickness of Al and N containing material from thefirst and second surfaces of the substrate, but because Al and Ncontaining material has been selectively deposited on the first surfacerelative to the second surface at step 320, at least some thickness ofAl and N containing material remains on the first surface of thesubstrate while substantially all or all of any Al and N containingmaterial that has been deposited on the second surface of the substrateis removed by the etch process at step 330.

In some embodiments etching the deposited Al and N containing materialat step 330 may comprise subjecting the deposited Al and N containingmaterial to a vapor etch process. In some embodiments the vapor etchprocess may be a cyclical vapor etch process. In some embodiments theetch process may comprise an atomic layer etch (ALE) process. In someembodiments a sub-monolayer or more of material can be removed from asubstrate by atomic layer etching (ALE) processes comprising contactingthe substrate surface in a reaction space with at least one vapor-phasereactant. In some embodiments one or more vapor-phase halide reactantsare used. The halide reactants may be metal halides, non-metal halides,semi-metal halides, semi/non-metal oxyhalides, or organic (oxy)halides.In some embodiments surface contamination may be removed from asubstrate surface, such as B or C contamination.

In some embodiments, ALE processes comprise alternately contacting thesubstrate surface in a reaction space with at least first and secondvapor-phase reactants. In some embodiments one or more of thevapor-phase reactants is a halide reactant. One or more etch cycles orsub-cycles may be provided in an ALE process as part of a selectivedeposition process or selective deposition super-cycle. In someembodiments the etch cycles comprise alternately exposing the substrateto two different reactants. In some embodiments the etch cycles compriseexposing the substrate to three different reactants. In some embodimentsthe etch cycles comprise exposing the substrate to four differentreactants. In some embodiments the etch cycles comprise exposing thesubstrate to more than four reactants. In some embodiments the reactantexposures are sequential. Each reactant exposure may be separated by apurge of the reaction space, or by pumping down the reaction chamber toremove reaction by products and excess reactant.

In some embodiments the substrate to be etched is exposed to one or morereactants selected from halides, oxygen compounds, oxygen scavengers,halide exchange drivers, ligand exchangers and metal organic orinorganic reactants. Oxygen compounds may comprise, for example, H₂O, O₂or O₃. Oxygen scavengers or halide exchange drivers may comprise, forexample, Ch_(y)Cl_(x) or CCl₄. In some embodiments an oxygen scavengeror halide exchange driver is a halide as described herein, including anon-metal or semi-metal halide. Ligand exchangers or metal or inorganicreactants may comprise, for example, Hacac or TMA/Sn(acac)₂. In someembodiments a ligand exchanger may be a halide as described herein,including a non-metal or semi-metal halide.

In some embodiments the etch cycles comprise a saturative, self-limitingadsorption step in which the substrate is contacted with at least onevapor phase reactant, such as a halide reactant. For example, thesubstrate may be contacted with a first vapor-phase reactant followed bya second exposure step in which the substrate is contacted with a secondvapor-phase reactant. In the first adsorption step the first reactantadsorbs in a self-limiting manner to the material to be etched on thesubstrate surface. The second exposure step then leads to the formationof volatile by-products that contain the adsorbate atoms, the secondprecursor atoms and some atoms from the surface being etched. In thisway the etching of the desired material on the substrate surface can becarefully controlled.

In some embodiments the reactions are not self-limiting. However,controlled etching may be achieved by supplying a controlled dose of oneor more of the reactants.

In some embodiments, gas phase reactions are avoided by feeding theprecursors alternatively and sequentially into the reaction chamber.Vapor phase reactants are separated from each other in the reactionchamber, for example, by removing excess reactants and/or reactionby-products from the reaction chamber between reactant pulses. Thereactants may be removed from proximity with the substrate surface withthe aid of a purge gas and/or vacuum. In some embodiments excessreactants and/or reactant byproducts are removed from the reaction spaceby purging, for example with an inert gas. Because of the separation ofreactants and the self-limiting nature of the reactions, less than amonolayer of material is typically removed in each ALE etch cycle.However, in some embodiments more than one monolayer may be removed ineach cycle. In some embodiments pulses of reactants may partially orcompletely overlap. For example, in some embodiments one reactant mayflow continuously into the reaction space while one or more additionalreactants are provided intermittently, at desired intervals.

In some embodiments the ALE methods disclosed herein are thermal etchingprocesses, as opposed to plasma etching processes. Thus, plasmareactants are not used in these thermal ALE etch cycles. While referredto as ‘thermal’ ALE processes to differentiate processes that use plasmareactants, in some embodiments the ALE reactions may have zeroactivation energy and therefore may not require any additional thermalenergy. Thus the reactions may also be referred to as chemical etchingprocesses. Thermal ALE methods can be more desirable in some situationsthan plasma ALE methods because thermal ALE methods can be less damagingto the underlying substrate. Also, thermal ALE methods can allow forisotropic etching of non-line of sight (NLOS) features.

However, in some embodiments the etch process may comprise an ALEprocess that does include plasma. In some embodiments an ALE process maycomprise contacting the deposited Al and N containing material with atleast one vapor phase etch reactant. In some embodiments the etchprocess may be a dry etch process, for example a reactive-ion etchingprocess. In some embodiments the dry etch process may be a thermal dryetch process. In some embodiments the dry etch process may include theuse of plasma.

In some embodiments the etch process of step 330 may comprise an ALEprocess comprising one or more etching sub-cycles comprising alternatelyand sequentially contacting the deposited Al and N containing materialwith a first vapor phase etch reactant and a second vapor phase etchreactant. In some embodiments the etching sub-cycle may be repeatedbetween 1 and 1000 times, between 1 and 500 times, between 1 and 300times, between 1 and 200 times, between 1 and 50 times, between 1 and100 times, or between 1 and 50 times.

In some embodiments the etch process of step 330 may comprise an ALEprocess comprising one or more etching sub-cycles comprising:

contacting the substrate with a first vapor phase etch reactant;

removing excess first etch reactant and reaction byproducts, if any,from the substrate;

contacting the substrate with a second vapor phase etch reactant;

removing excess second etch reactant and reaction byproducts, if any,from the substrate; and

optionally repeating the contacting and removing step to etch thedeposited Al and N containing material to a desired extent, for exampleuntil the deposited Al and N containing material is substantiallycompletely removed from the second surface of the substrate.

In some embodiments the etch process of step 330 may comprise an ALEprocess comprising one or more etching sub-cycles comprising:

contacting the substrate with a first vapor phase halide etch reactant,for example NF₃;

removing excess first etch reactant and reaction byproducts, if any,from the substrate;

contacting the substrate with a second vapor phase etch reactantcomprising Al, for example TMA;

removing excess second etch reactant and reaction byproducts, if any,from the substrate; and

optionally repeating the contacting and removing step to etch thedeposited Al and N containing material to a desired extent, for exampleuntil the deposited Al and N containing material is substantiallycompletely removed from the second surface of the substrate.

In some embodiments an etch sub-cycle may be repeated one or more times.Some embodiments involve the repetition of at least about 5 sub-cycles,at least about 10 sub-cycles, at least about 50 sub-cycles, at leastabout 100 sub-cycles, at least about 150 sub-cycles, at least about 200sub-cycles, at least about 300 sub-cycles, at least about 500sub-cycles, or at least about 1000 sub-cycles. In some embodiments anetch sub-cycle may be repeated until substantially all of the depositedAl and N containing material is removed from the second surface of thesubstrate while not all of the deposited Al and N containing material isremoved from the first surface of the substrate.

According to some embodiments, etch sub-cycles may be performed attemperatures ranging from about 20 to about 1200° C., about 50 to about800° C., about 75 to about 600° C., about 300° C. to about 500° C., orfrom about 350° C. to about 450° C. In some embodiments the temperatureis greater than about 20, 50 or 100° C., but less than about 1000, 800,600 or 500° C. In some embodiments the cycles are carried out at atemperature of about 450° C.

The pressure in the reaction chamber is typically from about 10⁻⁹ torrto about 760 ton, or about 0.001 to about 100 torr. However, in somecases the pressure will be higher or lower than this range, as can bedetermined by the skilled artisan given the particular circumstances. Insome embodiments a pressure of less than 2 ton is utilized.

In some embodiments an etch reactant contacts the substrate with thesurface to be etched for about 0.01 to about 60 seconds, about 0.05 toabout 30 seconds, about 0.05 seconds to about 5.0 seconds, about 0.1seconds to about 3 seconds or about 0.2 seconds to about 1.0 seconds. Insome embodiments an etch reactant contacts the substrate surface to beetched for about 0.05 seconds to about 5.0 seconds, about 0.1 seconds toabout 3 seconds or about 0.2 seconds to about 1.0 seconds. In someembodiments the contacting time may be greater than about 60 seconds.However, depending on the reactor type, material being etched and otherprocess conditions, such as surface area and temperature, an etchreactant contacting time may be even higher than about 10 seconds. Insome embodiments, contacting times can be on the order of minutes. Theoptimum contacting time can be readily determined by the skilled artisanbased on the particular circumstances.

In some embodiments excess etch reactant and reaction byproducts, ifany, can be removed from the substrate by, for example, purging thereaction chamber with an inert purge gas. In some embodiments thereaction chamber may be purged by stopping the flow of the etch reactantwhile continuing to flow a carrier gas or purge gas for a sufficienttime to diffuse or purge excess reactants and reactant by-products, fromthe reaction space. In some embodiments the excess etch reactant andreaction by-products are purged with the aid of inert gas, such ashelium or argon. In some embodiments the substrate may be moved from thereaction space containing the second reactant to a different reactionspace. The pulse of purge gas may, in some embodiments, be from about0.1 seconds to about 10 seconds, about 0.1 seconds to about 4 seconds orabout 0.1 seconds to about 0.5 seconds.

In some embodiments the first vapor phase etch reactant may comprise ahalide. In some embodiments the first vapor phase etch reactant maycomprise NF₃. In some embodiments the first vapor phase reactant maycomprise NbF₅. In some embodiments the first vapor phase etch reactantmay not comprise a plasma or an excited reactant. In some embodimentsthe second vapor phase etch reactant may comprise aluminum. In someembodiments the second vapor phase etch reactant may comprise one oftritertbutylaluminum (TTBA), trimethylaluminum (TMA) or triethylaluminum(TEA). In some embodiments the second vapor phase etch reactant may bethe same as a vapor phase precursor of the selectively depositing step320. In some embodiments the second vapor phase etch reactant maycomprise TMA. In some embodiments the second vapor phase etch reactantmay not comprise plasma or an excited reactant.

In some embodiments the etch step 330 is performed in the same reactionspace as the selective deposition step 320. However, in some embodimentsthe etch step 330 may be performed in a different reaction space than aselective deposition step 320. In some embodiments the selectivelydepositing AlN and the subjecting the substrate to an etch process stepsmay optionally be repeated at step 340 until an Al and N containingmaterial of a desired thickness has been formed on the first surface ofthe substrate relative to the second surface. That is, the super-cycle301 may optionally be repeated until Al and N containing material of adesired thickness has been formed on the first surface of the substraterelative to the second surface. In some embodiments the substrate is notexposed to ambient atmosphere after an etch step 330 and prior tobeginning another super-cycle 301. In some embodiments the substrate isnot exposed to air after an etch step 330 and prior to beginning anothersuper-cycle 301.

First Precursors

A number of different first precursors can be used in the selectivedeposition processes described herein as first precursors in a selectivedeposition cycle and/or selective deposition sub-cycle. In someembodiments the first precursor is an organometallic compound comprisingaluminum. In some embodiments the first precursor is an alkylaluminumcompound. In some embodiments the first precursor does not comprise anyother metals than aluminum.

In some embodiments the first precursor is a compound having the formulaR₃Al, where R is an alkyl group. Each R can be independently selectedfrom the list of: methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl,and tertbutyl groups. Preferably each R can be independently selectedfrom: methyl, ethyl and tertbutyl groups. In some embodiments, each Rcan be independently selected from C₁-C₄ alkyl groups.

In some embodiments the first precursor comprises Me₃Al, Et₃Al, or^(t)Bu₃Al. In some embodiments the first precursor istritertbutylaluminum (TTBA) As mentioned above, in some embodiments thefirst precursor is trimethylaluminum (TMA).

In some embodiments the first precursor is not a halide. In someembodiments the first precursor may comprise a halogen in at least oneligand, but not in all ligands. In some embodiments the first precursorcomprises one chlorine ligand and two alkyl ligands. In some embodimentsthe first precursor is AlCl₃.

In some embodiments the first precursor may comprise hydrogen as atleast one ligand, but not all ligands. In some embodiments the firstprecursor may comprise at least one hydrogen ligand and at least onealkyl ligand.

In some embodiments the first precursor does not comprise nitrogen. Insome embodiments the first precursor does not comprise silicon. In someembodiments the first precursor does not comprise oxygen. In someembodiments the first precursor does not comprise nitrogen, silicon, oroxygen.

Second Precursors

In some embodiments the second precursor comprises a nitrogen-hydrogenbond. In some embodiments the second precursor is ammonia (NH₃). In someembodiments, the second precursor is molecular nitrogen. In someembodiments the second precursor is a nitrogen containing plasma. Insome embodiments the second precursor is a nitrogen containing plasma,such as nitrogen and hydrogen containing plasma In some embodiments, thesecond precursor comprises an activated or excited nitrogen species. Insome embodiments the second precursor may be a provided in anitrogen-containing gas pulse that can be a mixture of nitrogen reactantand inactive gas, such as argon.

Integration

The Al and N containing material of the present disclosure may be usedin a variety of semiconductor applications. For example, Al and Ncontaining material may be particularly useful as an etch stop layer,for example a contact etch stop layer, in a self-aligned contactformation process. Self-aligned source/drain contacts can be used toprovide a misalignment margin for contact lithography. However, astandard self-aligned contact process requires additional processingsteps such as a multiple metal recess step, a SiN fill step, and a SiNpolish step using chemical-mechanical planarization.

In addition, the need for future scaling of the SiN sidewall spacer andetch stop layer in the standard self-aligned contact process due toincreasing device miniaturization may create a risk of short-circuitingbetween the contact and the metal gate due to spacer or etch stop layerover-etching.

In some embodiments an Al and N containing material of the presentdisclosure may be used as a etch stop layer in a self-aligned contactprocess that does not include a metal recess. In some embodiments an Alan N containing material of the present disclosure is etch resistant.FIG. 4 illustrates a process flow for a self-aligned contact processincluding an Al and N containing material protective layer, cappinglayer, or etch stop layer, according to some embodiments. In someembodiments a process for forming of a self-aligned contact 400 proceedsas follows:

a semiconductor substrate comprising a first surface and a second,different surface overlying a source/drain region is provided at step401;

an Al and N containing protective layer or etch stop layer, for exampleAlN, is selectively deposited on the first surface of the substraterelative to the second surface, at step 402;

the second surface is removed, for example using a wet etch process, atstep 403; and

a contact is formed in place of the removed second surface over asource/drain region of the substrate at step 404.

According to some embodiments, at step 401, a substrate comprising asemiconductor is provided. The semiconductor substrate comprises a firstsurface and a second, different surface. In some embodiments the firstsurface comprises a conductive surface. In some embodiments the firstsurface comprises one or more metal nitrides. In some embodiments thefirst surface may comprise the surface of a conductive gate and/or thesurface of a spacer. For example, in some embodiments the first surfacemay comprise a TiN gate and a SiN spacer. The second surface ispreferably a dielectric surface. In some embodiments the dielectriccomprises SiO₂. In some embodiments the second surface is a dummycontact overlying a source/drain region. In some embodiments the SiO₂dummy contact directly overlies a source/drain region.

In some embodiments the semiconductor substrate is subjected to astandard process through gate polish. That is, a semiconductor substratemay be subjected to a standard replaced metal gate process flow to forma source, gate, and drain as is well known in the art. In someembodiments a semiconductor substrate may be subjected to achemical-mechanical planarization process.

An Al and N containing protective layer or etch stop layer isselectively deposited on the first surface of the substrate relative tothe second surface at step 402. In some embodiments the Al an Ncontaining protective material is formed over a TiN gate and a SiNspacer. In some embodiments the Al and N containing protective materialis formed directly over a TiN gate and a SiN spacer.

In some embodiments the Al and N containing protective layer isdeposited by an ALD process as described herein. In some embodiments thesubstrate is alternately and sequentially contacted with a firstprecursor comprising Al and a second precursor comprising N. In someembodiments the Al and N containing protective layer comprises AlN. Insome embodiments the Al and N containing protective layer comprises anAlN thin film.

In some embodiments deposition of the Al and N containing protectivelayer on the first surface of the substrate relative to the secondsurface of the substrate is at least about 90% selective, at least about95% selective, at least about 96%, 97%, 98% or 99% or greater selective.In some embodiments deposition of the Al and N containing material onlyoccurs on the first surface and does not occur on the second surface. Insome embodiments deposition on the first surface of the substraterelative to the second surface of the substrate is at least about 80%selective, or at least about 50% selective.

In some embodiments, the Al and N containing protective layer or etchstop layer is deposited on the first surface of the substrate to achievea particular thickness. Suitable thicknesses may be greater than orequal to about 0.1 nm and less than or equal to about 10 nm. In someembodiments, the thickness will be between about 0.1 nm and about 5 nm.In some embodiments, the thickness will be between about 1 nm and about5 nm. In some embodiments, the thickness is between about 1 nm and about3 nm. In some embodiments, the thickness is between about 2 nm and about3 nm. Suitable thicknesses may be greater than or equal to about 0.1 nmand less than or equal to about 10 nm In some embodiments, the suitablethickness will be one that achieves a complete layer over the substratesurface (i.e., one that leaves no gaps). Accordingly, the actualthickness that achieves a complete layer may depend on the types ofprecursors used to achieve the Al and N containing material.

At step 403 the second surface of the substrate is removed, for exampleby using a wet etch process. In some embodiments the second surface ofthe substrate is removed by etching with dHF. For example, in someembodiments the first and second surfaces of the substrate are exposedto dHF and the second surface of the substrate is removed while the Aland N containing protective layer protects the underlying gate andspacer from being etched. The Al and N containing protective layer isable to function as a etch stop layer because it has a wet etch ratelower than that of the second, dielectric surface as described herein.

With continued reference to FIG. 4, at step 404 a contact may be formedover the source/drain region in place of the now removed second surface.In some embodiments a contact may be formed directly over thesource/drain region. In some embodiments a contact comprises a silicidematerial or a titanium containing material, for example Ti or TiN.According to some embodiments a contact may be formed according to anymethod known in the art or developed in the future. For example a Ticontact may be formed by physical vapor deposition (PVD) or a TiNcontact may be formed by atomic layer deposition (ALD).

In some embodiments after formation of the contact or contacts thesubstrate may then be optionally subjected to further processing ortreatment steps.

In some embodiments an Al and N containing material of the presentdisclosure may be used as a etch stop layer in a self-aligned contactprocess that does not include a metal recess. FIG. 5 illustrates aprocess flow for a self-aligned contact process including an Al and Ncontaining material protective layer, or etch stop layer, according tosome embodiments. In some embodiments a process for forming of aself-aligned contact 500 proceeds as follows:

a semiconductor substrate comprising a first surface and a second,different surface overlying a source/drain region is provided at step501;

a portion of the first surface is removed to create a recess therein atstep 502;

an Al and N containing protective layer or etch stop layer, for exampleAlN, is selectively deposited on the first surface of the substraterelative to the second surface, at step 503;

the second surface is removed, for example using a wet etch process, anda contact is formed in place of the removed second surface over asource/drain region of the substrate at step 504.

According to some embodiments, at step 501 a substrate comprising asemiconductor is provided. The semiconductor substrate comprises a firstsurface and a second, different surface. In some embodiments the firstsurface comprises a conductive surface. In some embodiments the firstsurface comprises one or more metal nitrides. In some embodiments thefirst surface may comprise the surface of a conductive gate and/or thesurface of a spacer. For example, in some embodiments the first surfacemay comprise a TiN gate and a SiN spacer. The second surface ispreferably a dielectric surface. In some embodiments the dielectriccomprises SiO₂. In some embodiments the second surface is a dummycontact overlying a source/drain region. In some embodiments the SiO₂dummy contact directly overlies a source/drain region.

In some embodiments the semiconductor substrate is subjected to astandard process through gate polish. That is, a semiconductor substratemay be subjected to a standard replaced metal gate process flow to forma source, gate, and drain as is well known in the art. In someembodiments a semiconductor substrate may be subjected to achemical-mechanical planarization process.

According to some embodiments, at step 502 a portion of the firstsurface is removed to create a recess therein. In some embodiments theportion of the first surface that is removed is a metal nitride. In someembodiments the portion of the first surface that is removed is SiN. Insome embodiments the portion of the first surface that is removed maycomprise a spacer, for example a SiN spacer. In some embodiments about0.1 nm to about 30 nm of a portion of the first surface is removed tocreate a recess with a depth of about 0.1 nm to about 30 nm. In someembodiments about 0.1 nm to about 20 nm of a portion of the firstsurface is removed to create a recess with a depth of about 0.1 nm toabout 20 nm. In some embodiments about 1 nm to about 10 nm of a portionof the first surface is removed to create a recess with a depth of about1 nm to about 10 nm.

An Al and N containing protective layer or etch stop layer is thenselectively deposited on the first surface of the substrate relative tothe second surface at step 503. In some embodiments the Al an Ncontaining protective material is formed over a TiN gate and a SiNspacer. In some embodiments the Al an N containing protective materialis formed directly over a TiN gate and a SiN spacer.

In some embodiments the Al and N containing protective layer isdeposited by an ALD process as described herein. In some embodiments thesubstrate is alternately and sequentially contacted with a firstprecursor comprising Al and a second precursor comprising N. In someembodiments the Al and N containing protective layer comprises AlN. Insome embodiments the Al and N containing protective layer comprises anAlN thin film.

Selectivity can be given as a percentage calculated by [(deposition onfirst surface)−(deposition on second surface)]/(deposition on the firstsurface). Deposition can be measured in any of a variety of ways. Insome embodiments deposition may be given as the measured thickness ofthe deposited material. In some embodiments deposition may be given asthe measured amount of material deposited. In some embodimentsdeposition of the Al and N containing protective layer on the firstsurface of the substrate relative to the second surface of the substrateis at least about 90% selective, at least about 95% selective, at leastabout 96%, 97%, 98% or 99% or greater selective. In some embodimentsdeposition of the Al and N containing material only occurs on the firstsurface and does not occur on the second surface. In some embodimentsdeposition on the first surface of the substrate relative to the secondsurface of the substrate is at least about 80% selective, or at leastabout 50% selective.

In some embodiments, the Al and N containing protective layer or etchstop layer is deposited on the first surface of the substrate to achievea particular thickness. Suitable thicknesses may be greater than orequal to 0.1 nm and less than or equal to about 10 nm. In someembodiments, the thickness will be between about 0.1 nm and about 5 nm.In some embodiments, the thickness will be between about 1 nm and about5 nm. In some embodiments, the thickness is between about 1 nm and about3 nm. In some embodiments, the thickness is between about 2 nm and about3 nm. Suitable thicknesses may be greater than or equal to about 0.1 nmand less than or equal to about 10 nm. In some embodiments, the suitablethickness will be one that achieves a complete layer over the substratesurface (i.e., one that leaves no gaps). Accordingly, the actualthickness that achieves a complete layer may depend on the types ofprecursors used to achieve the Al and N containing material.

At step 504 the second surface of the substrate is removed, for exampleby using a wet etch process. In some embodiments the second surface ofthe substrate is removed by etching with dHF. For example, in someembodiments the first and second surfaces of the substrate are exposedto dHF and the second surface of the substrate is removed while the Aland N containing protective layer protects the underlying gate andspacer from being etched. The Al and N containing protective layer isable to function as a etch stop layer because it has a wet etch ratelower than that of the second, dielectric surface as described herein. Acontact is then formed over the source/drain region in place of the nowremoved second surface. In some embodiments a contact may be formeddirectly over the source/drain region. In some embodiments a contactcomprises a silicide material, or a titanium containing material, forexample Ti or TiN. According to some embodiments a contact may be formedaccording to any method known in the art or developed in the future. Forexample a Ti contact may be formed by physical vapor deposition (PVD) ora TiN contact may be formed by atomic layer deposition (ALD).

In some embodiments after formation of the contact or contacts thesubstrate may then be optionally subjected to further processing ortreatment steps.

Example 1

In this example AlN was selectively deposited on the first surface of asubstrate relative to a second, different surface of the substrate. Inthis example the first surface of the substrate comprised TiN depositedby ALD and the second surface of the substrate comprised SiO₂ depositedby plasma enhanced vapor deposition (PEALD). Sample AlN films wereselectively deposited by an ALD process using trimethylaluminum (TMA) asa first precursor and NH₃ as a second precursor. Each deposition cyclewas carried out at a temperature of 375° C. and a reaction chamberpressure of 2 Torr. Each deposition cycle included a first precursorpulse of 0.5 seconds, and a second precursor pulse of 2 seconds. Aftereach TMA pulse the reaction chamber was purged for 3 seconds, and aftereach NH₃ pulse the reaction chamber was purged for 2 seconds.

Samples were deposited using an ALD process consisting of from 30 to 70deposition cycles. As illustrated in FIG. 6, the thicknesses of materialdeposited on the first, TiN surface was measured and compared with thethicknesses of material deposited on the second, SiO₂ surface. The ratioof material thickness deposited on the first TiN surface to the secondSiO₂ surface defines the selectivity of the deposition process. FIG. 6shows that for an ALD process consisting of 70 deposition cycles theratio of AlN deposited on the first surface relative to the secondsurface is approximately 8.5:1, which represents a selectivity of about89%.

Example 2

In this example AlN was selectively deposited on the first surface of asubstrate relative to a second, different surface of the substrate. Inthis example the first surface of the substrate comprised TiN depositedby ALD and the second surface of the substrate comprised SiO₂ depositedby PEALD. Further samples were prepared wherein AlN was selectivelydeposited on a first surface comprising TiN deposited by ALD relative toa second surface comprising native silicon oxide. Sample AlN films wereselectively deposited by an ALD process using trimethylaluminum (TMA) asa first precursor and NH₃ as a second precursor. Each deposition cyclewas carried out at a temperature of 375° C. and a reaction chamberpressure of 2 Ton. Each deposition cycle included a first precursorpulse of 0.5 seconds, and a second precursor pulse of 1 second. Aftereach TMA pulse the reaction chamber was purged for 3 seconds, and aftereach NH₃ pulse the reaction chamber was purged for 2 seconds.

Samples were deposited using an ALD process consisting of from 70 to 150deposition cycles. As illustrated in FIG. 7, the thicknesses of materialdeposited on the first, TiN surface was measured and compared with thethicknesses of material deposited on the second, SiO₂ and native oxidesurfaces. FIG. 7 shows that for an ALD process consisting of 130deposition cycles the ratio of AlN deposited on the first surfacerelative to the second PEALD SiO₂ surface is approximately 43:1, whichrepresents a selectivity of about 98%. For an ALD process consisting of110 deposition cycles the ratio of AlN deposited on the first surfacerelative to the second native oxide surface is approximately 3:1, whichrepresents a selectivity of about 75%.

Example 3

In this example AlN was selectively deposited on the first surface of asubstrate relative to a second, different surface of the substrate. Thefirst surface of the substrate comprised TiN deposited by ALD and thesecond surface of the substrate comprised native silicon oxide. Prior toAlN deposition, the substrate was subjected to a plasma treatmentprocess. The substrate was exposed to direct plasma generated at a powerof 50 W for 10 seconds. The plasma was generated from O₂.

The sample AlN film was selectively deposited by an ALD process usingtrimethylaluminum (TMA) as a first precursor and NH₃ as a secondprecursor. Each deposition cycle was carried out at a temperature of375° C. and a reaction chamber pressure of 2 Ton.

Each deposition cycle included a first precursor pulse of 0.5 seconds,and a second precursor pulse of 1 second. After each TMA pulse thereaction chamber was purged for 3 seconds, and after each NH₃ pulse thereaction chamber was purged for 2 seconds. The sample was depositedusing an ALD process consisting of 110 deposition cycles.

Referring now to FIG. 8, the thickness of the material deposited on thefirst plasma treated TiN surface was measure and compared with thethickness of material deposited on the second plasma treated nativeoxide surface. FIG. 8 also shows the data obtained from the samples inExample 2. No significant change in AlN thickness is observed whencomparing the thickness of material deposited on the first TiN surfaceafter 110 deposition cycles with the thickness of material deposited onthe first plasma treated TiN surface after 110 deposition cycles.However, a significant reduction in AlN thickness is observed whencomparing the thickness of material deposited on the second native oxidesurface after 110 deposition cycles with the thickness of materialdeposited on the second plasma treated native oxide surface. Afterplasma treatment, essentially no deposition is observed on the secondsurface relative to the first surface. For an ALD process consisting of110 deposition cycles the ratio of AlN deposited on the first plasmatreated TiN surface relative to the second plasma treated native oxidesurface is approximately 33:1, which is over a 10× improvement inselectivity when compared to an identical selective deposition processwithout plasma treatment.

Further samples were prepared wherein the first surface of the substratecomprised TiN deposited by ALD and the second surface of the substratecomprised native silicon oxide. Prior to AlN deposition, the substrateswere subjected to a plasma treatment process. The substrates wereexposed to direct plasma generated at a power of between 50 W and 300 Wfor between 3 seconds and 10 seconds. The plasma was generated from 02.The thicknesses of AlN deposited on the first surface of each substratewere compared with the thicknesses of material deposited on the secondsurface and the selectivity was calculated for each sample. Results areshown in Table 1, below.

TABLE 1 Selectivity of AlN deposited by ALD with varying direct plasmatreatment conditions O2 Direct Thickness Plasma Thickness of AlN O2Plasma Exposure of AlN deposited Power Time No. of deposited on NativeSelec- (Watts) (Seconds) Cycles on TiN (nm) Oxide (nm) tivity 50 10 1105.21 0.16 32.6 300 10 110 4.36 0.2 21.8 300 3 110 4.40 0.43 10.2

From these results, it was observed that selectivity of AlN depositiondecreased as the power of the direct plasma pretreatment increased,while the selectivity was observed to increase with increasing directplasma exposure duration.

Example 4

In this example AlN was selectively deposited on the first surface of asubstrate relative to a second, different surface of the substrate. Inthis example the first surface of the substrate comprised TiN depositedby ALD and the second surface of the substrate comprised SiO₂ depositedby PEALD. Further samples were prepared wherein AlN was selectivelydeposited on a first surface comprising TiN deposited by ALD relative toa second surface comprising SiO₂ deposited by PEALD. Sample AlN filmswere selectively deposited by an ALD process using trimethylaluminum(TMA) as a first precursor and NH₃ as a second precursor. Eachdeposition cycle was carried out at a temperature of 390° C. and areaction chamber pressure of 2 Torr. Each deposition cycle included afirst precursor pulse of 0.5 seconds, and a second precursor pulse of 1second. After each TMA pulse the reaction chamber was purged for 5seconds, and after each NH₃ pulse the reaction chamber was also purgedfor 5 seconds.

Samples were deposited using an ALD process consisting of from 70 to 100deposition cycles. As illustrated in FIG. 9, the thicknesses of materialdeposited on the first, TiN and W surfaces was measured and comparedwith the thicknesses of material deposited on the second, SiO₂ surface.FIG. 9 shows that AlN deposition on a first surface comprising either Wor TiN had very high selectivity relative to the SiO₂ surface.

Example 5

In this example, AlN was selectively formed on the first surface of asubstrate relative to a second, different surface of the same substrate.In this example the substrate comprised a W/SiO₂ pattern structure,wherein the first surface of the substrate comprised W metal lines thathad been formed on a silicon wafer. The second surface of the substratecomprised SiO₂ deposited by plasma enhanced chemical vapor deposition(PECVD). Sample AlN films were formed on the first surface of thesubstrate by a process as described herein, for example with respect toFIG. 3, comprising a super-cycle comprising pretreating the substrate,selectively depositing AlN on the first surface relative to the secondsurface, and etching the deposited AlN such that substantially all ofthe deposited AlN was removed from the second surface and notsubstantially all of the deposited AlN was removed from the firstsurface. The process comprised four super-cycles.

The pretreatment step comprised exposing the substrate to a plasmagenerated from H₂ at a temperature of 250° C. according to someembodiments and as described herein. The selective deposition stepcomprised an ALD process comprising a plurality of sub-cycles comprisingalternately and sequentially contacting the substrate with a first vaporphase precursor comprising TMA and a second vapor phase precursorcomprising NH₃ at a process temperature of 375° C., according to someembodiments and as described herein. The etch step comprise an ALEprocess a plurality of sub-cycles comprising alternately andsequentially contacting the substrate with a first vapor phase etchreactant comprising NF₃ and a second vapor phase etch reactantcomprising TMA at a process temperature of 300° C. The sub-cycles wererepeated until substantially all of the deposited AlN was removed fromthe second surface and not substantially all of the deposited AlN wasremoved from the first surface.

FIG. 10A shows a scanning electron microscope (SEM) image of thedeposited AlN film. It was observed that approximately 15 nm of AlN wasformed on the first surface comprising W, while no observable AlN wasformed on the second surface comprising SiO₂. FIG. 10B is an enhancedview of a portion of the substrate, showing a single W line. An AlN filmcan clearly be observed on the W surface, while no AlN is observed onthe adjacent SiO₂ surface.

Language of degree used herein, such as the terms “approximately,”“about,” “generally,” and “substantially” as used herein represent avalue, amount, or characteristic close to the stated value, amount, orcharacteristic that still performs a desired function or achieves adesired result. For example, the terms “approximately”, “about”,“generally,” and “substantially” may refer to an amount that is withinless than or equal to 10% of, within less than or equal to 5% of, withinless than or equal to 1% of, within less than or equal to 0.1% of, andwithin less than or equal to 0.01% of the stated amount. If the statedamount is 0 (e.g., none, having no), the above recited ranges can bespecific ranges, and not within a particular % of the value. Forexample, within less than or equal to 10 wt./vol. % of, within less thanor equal to 5 wt./vol. % of, within less than or equal to 1 wt./vol. %of, within less than or equal to 0.1 wt./vol. % of, and within less thanor equal to 0.01 wt./vol. % of the stated amount.

The terms “film” and “thin film” are used herein for simplicity. “Film”and “thin film” are meant to mean any continuous or non-continuousstructures and material deposited by the methods disclosed herein. Forexample, “film” and “thin film” could include 2D materials, nanorods,nanotubes or nanoparticles or even single partial or full molecularlayers or partial or full atomic layers or clusters of atoms and/ormolecules. “Film” and “thin film” may comprise material or layer withpinholes, but still be at least partially continuous.

It will be understood by those of skill in the art that numerous andvarious modifications can be made without departing from the spirit ofthe present invention. The described features, structures,characteristics and precursors can be combined in any suitable manner.Therefore, it should be clearly understood that the forms of the presentinvention are illustrative only and are not intended to limit the scopeof the present invention. All modifications and changes are intended tofall within the scope of the invention, as defined by the appendedclaims.

1. (canceled)
 2. A process for selectively forming AlN on a firstsurface of a substrate relative to a second different surface of thesubstrate, the process comprising one or more super-cycles comprising:selectively depositing AlN on the first surface relative to the seconddifferent surface of the substrate by one or more selective depositionsub-cycles; etching the deposited AlN by one or more thermal etchingsub-cycles; wherein AlN is selectively formed on the first surface ofthe substrate relative to the second different surface of the substratewith a selectivity greater than about 99%.
 3. The process of claim 2,wherein the super-cycle is repeated until an AlN thin film of a desiredthickness is formed on the first surface of the substrate.
 4. Theprocess of claim 2, additionally comprising exposing the substrate to apretreatment reactant.
 5. The process of claim 4, the super-cyclefurther comprising exposing the substrate to a pretreatment reactantprior to selectively depositing AlN.
 6. The process of claim 4, whereinthe pretreatment reactant comprises plasma.
 7. The process of claim 6,wherein the plasma is generated from a gas comprising H₂.
 8. The processof claim 2, wherein the one or more selective deposition sub-cyclescomprise: contacting the substrate with a first vapor phase precursorcomprising aluminum; and contacting the substrate with a second vaporphase precursor comprising nitrogen.
 9. The process of claim 8, whereinAlN is deposited on the first surface of the substrate relative to thesecond surface of the substrate with a selectivity of greater than 5% inthe one or more selective deposition sub-cycles.
 10. The process ofclaim 8, wherein the one or more selective deposition sub-cycles arerepeated until the one or more selective deposition sub-cycles are nolonger selective.
 11. The process of claim 8, wherein the first vaporphase precursor comprising aluminum comprises tritertbutylaluminum(TTBA), trimethylaluminum (TMA) or triethylaluminum (TEA).
 12. Theprocess of claim 8, wherein the second vapor phase precursor comprisingnitrogen comprises NH₃.
 13. The process of claim 2, wherein the one ormore thermal etching sub-cycles comprise: contacting the substrate witha first vapor phase halide etch reactant; and contacting the substratewith a second vapor phase etch reactant comprising aluminum.
 14. Theprocess of claim 13, wherein the first vapor phase halide etch reactantcomprises NF₃ or NbF₅.
 15. The process of claim 13, wherein the secondvapor phase etch reactant comprising aluminum comprisestrimethylaluminum (TMA) or triethylaluminum (TEA).
 16. The process ofclaim 13, wherein the one or more thermal etching sub-cycles are carriedout at a process temperature of about 300° C.
 17. The process of claim2, wherein the first surface is a conductive surface and the seconddifferent surface is a dielectric surface.
 18. The process of claim 2,wherein the first surface comprises W and the second surface comprisesSiO₂.
 19. The process of claim 2, wherein the first surface comprisesTiN and the second surface comprises SiO₂.
 20. The process of claim 2,wherein the selective deposition sub-cycle is repeated from 1 to about300 times and the thermal etching sub-cycle is repeated from 1 to about150 times.
 21. The process of claim 2, wherein the one or more selectivedeposition sub-cycles comprise contacting the substrate with a firstvapor phase precursor comprising trimethylaluminum (TMA) and contactingthe substrate with a second vapor phase precursor comprising NH₃, andthe one or more thermal etching sub-cycles comprise contacting thesubstrate with a the first vapor phase halide etch reactant comprisingNF₃, and a second vapor phase etch reactant comprising TMA.